Chemistry of In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub> and Some Heteroleptic
Organoindium(III) Derivatives. Crystal and Molecular
Structures of In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub>, (C<sub>5</sub>H<sub>5</sub>)<sub>3</sub>In·PPh<sub>3</sub>, and
(Me<sub>3</sub>CCH<sub>2</sub>)<sub>2</sub>In(C<sub>5</sub>H<sub>5</sub>)

Pure In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub> has been prepared in high yields from InCl<sub>3</sub> and Li(C<sub>5</sub>H<sub>5</sub>) in THF solution
with the absence of external heating. Neat In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub> readily decomposes at 150 °C to form
In(C<sub>5</sub>H<sub>5</sub>)<sub>(s)</sub> and cyclopentadiene as the primary products whereas a benzene suspension
decomposes under refluxing conditions. In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub> forms an isolable 1:1 adduct with PPh<sub>3</sub>
but NMe<sub>3</sub>, THF, and Et<sub>2</sub>O do not form stable adducts. Ligand redistribution reactions with
InR<sub>3</sub> (R = Me and CH<sub>2</sub>CMe<sub>3</sub>) in THF solution provided R<sub>2</sub>In(C<sub>5</sub>H<sub>5</sub>) and RIn(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>. These
heteroleptic organoindium(III) compounds have been isolated as analytically pure crystalline
solids, but in THF solution they form equilibrium mixtures of the adducts of InR<sub>3</sub>, R<sub>2</sub>In(C<sub>5</sub>H<sub>5</sub>), RIn(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>, and In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub>, as appropriate. Crystals of [In(C<sub>5</sub>H<sub>5</sub>)<sub>3</sub>]<i><sub>n</sub></i>, (C<sub>5</sub>H<sub>5</sub>)<sub>3</sub>In·PPh<sub>3</sub>,
and [(Me<sub>3</sub>CCH<sub>2</sub>)<sub>2</sub>In(C<sub>5</sub>H<sub>5</sub>)]<i><sub>n</sub></i> were characterized by single-crystal X-ray structural studies.